Gas analysis - Conversion of gas mixture composition data (ISO 14912:2003)

This International Standard defines the following quantities commonly used to express the composition of gas mixtures: - mole fraction, - mass fraction, - volume fraction, and - mole concentration, - mass concentration, - volume concentration. For these quantities of composition, this International Standard provides methods for conversion between different quantities, and conversion between different state conditions. Conversion between different quantities means calculating the numerical value of an analyte content in terms of one of the quantities listed above from the numerical value of the same analyte content, at the same pressure and temperature of the gas mixture, given in terms of another of these quantities. Conversion between different state conditions means calculating the numerical value of an analyte content, in terms of one of the quantities listed above, under one set of state conditions from the numerical value of the same quantity under another set of state conditions, i.e. pressure and temperature, of the gas mixture. Gas mixture composition can be converted simultaneously between different quantities of composition and different state composition can be converted simultaneously between different quantities of composition and different state conditions by combination of the two types of conversion. This International Standard is applicable only to homogeneous and stable gas mixtures. Therefore any state conditions (pressure and temperature) considered need to be well outside the condensation region of the gas mixture and that of each of the specified analytes (see Annex A).

Gasanalyse - Umrechnung von Zusammensetzungsangaben für Gasgemische (ISO 14912:2003)

Diese Internationale Norm definiert die folgenden Größen, die zur Angabe der Zusammensetzung von
Gasgemischen verwendet werden:
- Stoffmengenanteil,
- Massenanteil,
- Volumenanteil,
sowie
- Stoffmengenkonzentration,
- Massenkonzentration,
- Volumenkonzentration.
Für die genannten Zusammensetzungsgrößen legt diese Internationale Norm Verfahren fest zur
- Umrechnung zwischen verschiedenen Größen, und
- Umrechnung zwischen verschiedenen Zustandsbedingungen.
Umrechnung zwischen verschiedenen Größen bedeutet: Berechnung des Zahlenwerts eines Analytgehalts in
einer der oben genannten Größen aus dem Zahlenwert desselben Analytgehalts, gegeben in einer anderen
dieser Größen, bei gleichem Druck und gleicher Temperatur des Gasgemischs. Umrechnung zwischen
verschiedenen Zustandsbedingungen bedeutet: Berechnung des Zahlenwerts eines Analytgehalts in einer der
oben genannten Größen bei einem Satz von Zustandsbedingungen aus dem Zahlenwert derselben Größe bei
einem anderen Satz von Zustandsbedingungen, d. h. Druck und Temperatur des Gasgemischs. Durch
Kombination dieser beiden Umrechnungsarten kann die Zusammensetzung von Gasgemischen zugleich
zwischen verschiedenen Zusammensetzungsgrößen und verschiedenen Zustandsbedingungen umgerechnet
werden.
Diese Internationale Norm ist nur bei homogenen und stabilen Gasgemischen anwendbar. Deshalb müssen
die betrachteten Zustandsbedingungen mit deutlichem Abstand außerhalb der Kondensationsgebiete des
Gasgemischs sowie jedes der angegeben Analyten liegen (siehe Anhang A).

Analyse des gaz - Conversion des données de composition de mélanges gazeux (ISO 14912:2003)

Analiza plinov – Pretvorba podatkov sestave plinskih zmesi (ISO 14912:2003)

General Information

Status
Published
Publication Date
31-Oct-2006
Current Stage
6060 - National Implementation/Publication (Adopted Project)
Start Date
01-Nov-2006
Due Date
01-Nov-2006
Completion Date
01-Nov-2006

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SLOVENSKI STANDARD
SIST EN ISO 14912:2006
01-november-2006
Analiza plinov – Pretvorba podatkov sestave plinskih zmesi (ISO 14912:2003)
Gas analysis - Conversion of gas mixture composition data (ISO 14912:2003)
Gasanalyse - Umrechnung von Zusammensetzungsangaben für Gasgemische (ISO
14912:2003)
Analyse des gaz - Conversion des données de composition de mélanges gazeux (ISO
14912:2003)
Ta slovenski standard je istoveten z: EN ISO 14912:2006
ICS:
71.040.40
SIST EN ISO 14912:2006 en
2003-01.Slovenski inštitut za standardizacijo. Razmnoževanje celote ali delov tega standarda ni dovoljeno.

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EUROPEAN STANDARD
EN ISO 14912
NORME EUROPÉENNE
EUROPÄISCHE NORM
August 2006
ICS 71.040.40

English Version
Gas analysis - Conversion of gas mixture composition data (ISO
14912:2003)
Analyse des gaz - Conversion des données de composition Gasanalyse - Umrechnung von
de mélanges gazeux (ISO 14912:2003) Zusammensetzungsangaben für Gasgemische (ISO
14912:2003)
This European Standard was approved by CEN on 21 July 2006.
CEN members are bound to comply with the CEN/CENELEC Internal Regulations which stipulate the conditions for giving this European
Standard the status of a national standard without any alteration. Up-to-date lists and bibliographical references concerning such national
standards may be obtained on application to the Central Secretariat or to any CEN member.
This European Standard exists in three official versions (English, French, German). A version in any other language made by translation
under the responsibility of a CEN member into its own language and notified to the Central Secretariat has the same status as the official
versions.
CEN members are the national standards bodies of Austria, Belgium, Cyprus, Czech Republic, Denmark, Estonia, Finland, France,
Germany, Greece, Hungary, Iceland, Ireland, Italy, Latvia, Lithuania, Luxembourg, Malta, Netherlands, Norway, Poland, Portugal, Romania,
Slovakia, Slovenia, Spain, Sweden, Switzerland and United Kingdom.
EUROPEAN COMMITTEE FOR STANDARDIZATION
COMITÉ EUROPÉEN DE NORMALISATION
EUROPÄISCHES KOMITEE FÜR NORMUNG
Management Centre: rue de Stassart, 36  B-1050 Brussels
© 2006 CEN All rights of exploitation in any form and by any means reserved Ref. No. EN ISO 14912:2006: E
worldwide for CEN national Members.

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EN ISO 14912:2006 (E)



Foreword

The text of ISO 14912:2003 has been prepared by Technical Committee ISO/TC 158
"Analysis of gases” of the International Organization for Standardization (ISO) and has been
taken over as EN ISO 14912:2006 by Technical Committee CEN/SS N21 "Gaseous fuels and
combustible gas", the secretariat of which is held by CMC.

This European Standard shall be given the status of a national standard, either by publication
of an identical text or by endorsement, at the latest by February 2007, and conflicting national
standards shall be withdrawn at the latest by February 2007.

According to the CEN/CENELEC Internal Regulations, the national standards organizations of
the following countries are bound to implement this European Standard: Austria, Belgium,
Cyprus, Czech Republic, Denmark, Estonia, Finland, France, Germany, Greece, Hungary,
Iceland, Ireland, Italy, Latvia, Lithuania, Luxembourg, Malta, Netherlands, Norway, Poland,
Portugal, Romania, Slovakia, Slovenia, Spain, Sweden, Switzerland and United Kingdom.



Endorsement notice

The text of ISO 14912:2003 has been approved by CEN as EN ISO 14912:2006 without any
modifications.


2

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INTERNATIONAL ISO
STANDARD 14912
First edition
2003-03-15

Gas analysis — Conversion of gas
mixture composition data
Analyse des gaz — Conversion des données de composition de
mélanges gazeux




Reference number
ISO 14912:2003(E)
©
ISO 2003

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ISO 14912:2003(E)
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ii © ISO 2003 — All rights reserved

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ISO 14912:2003(E)
Contents Page
Foreword .iv
Introduction.v
1 Scope.1
2 Terms and definitions .1
3 Symbols and units .4
4 Basic principles.6
4.1 Expression of gas mixture composition.6
4.2 Conversion between different quantities.8
4.3 Conversion between different state conditions.9
5 Main procedures.10
5.1 Conversion between different quantities of composition.10
5.2 Conversion to reference conditions.13
6 Practical implementation.13
6.1 Conversion between quantities of composition .13
6.2 Conversion of single analyte contents .14
6.3 Conversion of complete compositions.15
6.4 Conversion between state conditions .15
6.5 Simple approximations applicable to conversion .15
7 Input quantities and their uncertainties.16
7.1 Pure gas data.16
7.2 Gas mixture data .19
7.3 Rough uncertainty estimates.22
8 Conversion uncertainty .22
8.1 General considerations .22
8.2 Conversion of single analyte contents .23
8.3 Conversion of complete compositions.24
8.4 Uncertainty calculation using numerical differentiation.26
8.5 Variances and covariances of input composition data.27
9 Application recommendations.29
Annex A (normative) Assessment of state conditions .30
Annex B (normative) Summation relations for the expression of mixture properties .33
Annex C (informative) Mixture component data .34
Annex D (informative) Examples.40
Annex E (informative) Computer implementation of recommended methods.55
Bibliography.57

© ISO 2003 — All rights reserved iii

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ISO 14912:2003(E)
Foreword
ISO (the International Organization for Standardization) is a worldwide federation of national standards bodies
(ISO member bodies). The work of preparing International Standards is normally carried out through ISO
technical committees. Each member body interested in a subject for which a technical committee has been
established has the right to be represented on that committee. International organizations, governmental and
non-governmental, in liaison with ISO, also take part in the work. ISO collaborates closely with the
International Electrotechnical Commission (IEC) on all matters of electrotechnical standardization.
International Standards are drafted in accordance with the rules given in the ISO/IEC Directives, Part 2.
The main task of technical committees is to prepare International Standards. Draft International Standards
adopted by the technical committees are circulated to the member bodies for voting. Publication as an
International Standard requires approval by at least 75 % of the member bodies casting a vote.
Attention is drawn to the possibility that some of the elements of this document may be the subject of patent
rights. ISO shall not be held responsible for identifying any or all such patent rights.
ISO 14912 was prepared by Technical Committee ISO/TC 158, Analysis of gases.
iv © ISO 2003 — All rights reserved

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ISO 14912:2003(E)
Introduction
The objective of gas analysis is to determine the composition of gas mixtures. Gas mixture composition is
expressed qualitatively in terms of specified mixture components of interest, called analytes, and the
complementary gas. Gas mixture composition is expressed quantitatively by specifying the amount of every
analyte in the mixture and the composition of the complementary gas.
For the purpose of specifying the amount of an analyte in a gas mixture, different quantities are in use. This
diversity is due to the fact that in different applications different quantities have decisive advantages.
Therefore procedures for conversion between different quantities are required.
In cases where these quantities involve the volumes of the analytes or the gas mixture or both, they depend
on the state conditions, i.e. pressure and temperature, of the gas mixture. For each of these quantities,
procedures for conversion between different state conditions are required.
As a crude approximation, all of the conversions referred to above can be performed on the basis of the Ideal
Gas Law. In most cases, however, an accurate conversion has to take into account the real gas volumetric
behaviour of the analyte and of the gas mixture. In particular, many conversions require values of the
compression factor (or of the density) of the gas mixture.
This International Standard provides formally exact conversion procedures, based on fundamental principles,
which fully account for real gas behaviour of pure gases and gas mixtures. In addition to these, approximate
procedures for practical applications are described, designed for different levels of accuracy and available
data. These approximations are necessary because measured gas mixture compression factors (or densities)
are rarely available and therefore have to be estimated from component data. Uncertainty estimates are given
which result from combining approximations in the conversion procedures with the uncertainties of the input
data. Where conversions require real-gas volumetric data of pure gases or gas mixtures, these are expressed
by compression factors. As equivalents, density data could be converted into compression factor data.
© ISO 2003 — All rights reserved v

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INTERNATIONAL STANDARD ISO 14912:2003(E)

Gas analysis — Conversion of gas mixture composition data
1 Scope
This International Standard defines the following quantities commonly used to express the composition of gas
mixtures:
 mole fraction,
 mass fraction,
 volume fraction,
and
 mole concentration,
 mass concentration,
 volume concentration.
For these quantities of composition, this International Standard provides methods for
 conversion between different quantities, and
 conversion between different state conditions.
Conversion between different quantities means calculating the numerical value of an analyte content in terms
of one of the quantities listed above from the numerical value of the same analyte content, at the same
pressure and temperature of the gas mixture, given in terms of another of these quantities. Conversion
between different state conditions means calculating the numerical value of an analyte content, in terms of
one of the quantities listed above, under one set of state conditions from the numerical value of the same
quantity under another set of state conditions, i.e. pressure and temperature, of the gas mixture. Gas mixture
composition can be converted simultaneously between different quantities of composition and different state
conditions by combination of the two types of conversion.
This International Standard is applicable only to homogeneous and stable gas mixtures. Therefore any state
conditions (pressure and temperature) considered need to be well outside the condensation region of the gas
mixture and that of each of the specified analytes (see Annex A).
2 Terms and definitions
For the purpose of this document, the following terms and definitions apply.
NOTE See also References [1] and [2] in the Bibliography.
2.1 Quantities for the expression of gas mixture composition
NOTE Further information concerning the terms defined in this subclause is given in 4.1.
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ISO 14912:2003(E)
2.1.1
mole fraction
amount-of-substance fraction
x
quotient of the amount of substance of a specified component and the sum of the amounts of substance of all
components of a gas mixture
NOTE The mole fraction is independent of the pressure and the temperature of the gas mixture.
2.1.2
mass fraction
w
quotient of the mass of a specified component and the sum of the masses of all components of a gas mixture
NOTE The mass fraction is independent of the pressure and the temperature of the gas mixture.
2.1.3
volume fraction
φ
quotient of the volume of a specified component and the sum of the volumes of all components of a gas
mixture before mixing, all volumes referring to the pressure and the temperature of the gas mixture
NOTE The volume fraction is not independent of the pressure and the temperature of the gas mixture. Therefore the
pressure and the temperature have to be specified.
2.1.4
mole concentration
amount-of-substance concentration
c
quotient of the amount of substance of a specified component and the volume of a gas mixture
NOTE The mole concentration is not independent of the pressure and the temperature of the gas mixture. Therefore
the pressure and the temperature have to be specified.
2.1.5
mass concentration
β
quotient of the mass of a specified component and the volume of a gas mixture
NOTE The mass concentration is not independent of the pressure and the temperature of the gas mixture. Therefore
the pressure and the temperature have to be specified.
2.1.6
volume concentration
σ
quotient of the volume of a specified component before mixing and the volume of a gas mixture, both volumes
referring to the same pressure and the same temperature
NOTE 1 The volume concentration is not independent of the pressure and the temperature of the gas mixture.
Therefore the pressure and the temperature have to be specified.
NOTE 2 The volume fraction (2.1.3) and volume concentration (2.1.6) take the same value if, at the same state
conditions, the sum of the component volumes before mixing and the volume of the mixture are equal. However, because
the mixing of two or more gases at the same state conditions is usually accompanied by a slight contraction or, less
frequently, a slight expansion, this is not generally the case.
2 © ISO 2003 — All rights reserved

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ISO 14912:2003(E)
2.2 Additional quantities involved in conversions of gas mixture composition
2.2.1
compression factor
Z
quotient of the volume of an arbitrary amount of gas at specified pressure and temperature and the volume of
the same amount of gas, at the same state conditions, as calculated from the ideal gas law
NOTE 1 This definition is applicable to pure gases and to gas mixtures, therefore the term “gas” is used as a general
term which covers pure gases as well as gas mixtures.
NOTE 2 By definition, the compression factor of an ideal gas is 1. At room temperature and atmospheric pressure, for
many gases the compression factor differs only moderately from 1.
2.2.2
mixing factor
f
quotient of the volume of an arbitrary amount of a gas mixture at specified pressure and temperature and the
sum of the volumes of all mixture components, before mixing, at the same state conditions
NOTE If the component volumes are strictly additive, i.e. if the sum of the component volumes before mixing is the
same as the volume after mixing, the mixing factor is 1. At room temperature and atmospheric pressure, for many gas
mixtures the mixing factor differs only slightly from 1.
2.2.3
density
ρ
quotient of the mass of an arbitrary amount of gas and its volume at specified pressure and temperature
NOTE This definition is applicable to pure gases and to gas mixtures, therefore the term “gas” is used as a general
term which covers pure gases as well as gas mixtures.
2.2.4
molar volume
V
mol
quotient of the volume of an arbitrary amount of gas at specified pressure and temperature and its amount of
substance
NOTE 1 This definition is applicable to pure gases and to gas mixtures, therefore the term “gas” is used as a general
term which covers pure gases as well as gas mixtures.
NOTE 2 The amount of substance of a mixture is given by the sum of the amounts of substance of the components.
2.2.5
virial coefficients
coefficients in the expansion of the compression factor in terms of powers of a quantity of state
NOTE In practice, only two virial expansions are used, where the quantity of state is either the pressure, p, or the
inverse molar volume, 1/V , as follows.
mol
BT() C()T
ZV ,1T =+ + + . (1)
()
mol
2
V
V
mol
mol
2
Zp,T =+1 B′′T p+C T p + . (2)
() () ()
© ISO 2003 — All rights reserved 3

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ISO 14912:2003(E)
2.2.5.1
second molar-volume virial coefficient
B
coefficient of 1/V in the expansion of the compression factor in terms of inverse powers of the molar
mol
volume, V
mol
2.2.5.2
third molar-volume virial coefficient
C
2
coefficient of 1/V in the expansion of the compression factor in terms of inverse powers of the molar
mol
volume, V
mol
2.2.5.3
second pressure virial coefficient
B′
coefficient of p in the expansion of the compression factor in terms of powers of the pressure p
2.2.5.4
third pressure virial coefficient
C′
2
coefficient of p in the expansion of the compression factor in terms of powers of the pressure p
3 Symbols and units
Symbol Quantity SI unit
3
abbreviation of p/(RT)
α
mol/m
3
B second molar-volume virial coefficient
m /mol
B′ second pressure virial coefficient 1/Pa
3
mass concentration
β kg/m
3
c mole concentration
mol/m
6 2
C third molar-volume virial coefficient
m /mol
2
C′ third pressure virial coefficient
1/Pa
D dilution factor 1
f mixing factor 1
volume fraction 1
φ
i
gas mixture components (i = 1, 2, …, N) —
j, k gas mixture components (from 1 to N) —
(where needed in addition to symbol i)
m mass kg
M molar mass kg/mol
n amount of substance mol
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ISO 14912:2003(E)
Symbol Quantity SI unit
N
number of gas mixture components —
p pressure Pa
p saturation vapour pressure Pa
vap
p dew pressure Pa
dew
R molar gas constant (8,314 510)
J/(mol⋅K)
3
density
ρ kg/m
S
(sample of) gas mixture —
3 3
volume concentration
σ m /m
t Celsius temperature °C
T thermodynamic temperature K
3
V volume
m
3
V molar volume
m /mol
mol
w mass fraction 1
W weight (of a gas cylinder) kg
x mole fraction 1
X reference value of state conditions (X = p, T) same as for X
ref
X critical component property (X = p, T, V, Z) same as for X
crit
X pseudo-critical mixture property (X = p, T) same as for X
pscrit
Z compression factor 1

In addition to the symbols specified above, the following symbols are used to denote objects of generic
mathematical expressions.
© ISO 2003 — All rights reserved 5

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ISO 14912:2003(E)
Symbol Quantity
F mathematical function expressing a conversion
I input quantity of composition
O output quantity of composition
Ω conversion factor
K,L,P,Q,Y general variables or quantities
∂F/∂P partial derivative (sensitivity coefficient)
r(P,Q) correlation coefficient of quantities P,Q
R correlation matrix
u(P) standard uncertainty of quantity P
2
u (P) variance of quantity P
u(P,Q) covariance of quantities P,Q
U variance/covariance matrix
v(P) relative standard uncertainty of quantity P
4 Basic principles
4.1 Expression of gas mixture composition
The generic term for the amount of a component in a mixture is “content”. This term is intended for use only in
a purely descriptive or qualitative sense, and is, without further qualification, inappropriate and insufficient to
express quantitatively the amount of a component.
Quantitative statements require the expression of content as a value (the product of a number and a unit) of a
“quantity of composition”.
For present purposes, six quantities of composition, subdivided into two distinct conceptual families, called
fractions and concentrations, are defined in 2.1. The terms “fraction” and “concentration” are themselves
incomplete, and cannot be used in quantitative statements of content without qualification by one of the
modifiers “mole”, “mass” or “volume”.
In quantitative expressions of gas mixture composition, the applicable quantity, for example the mole fraction
or the mass concentration, shall be used in conjunction with the name or the chemical symbol of the
component.
EXAMPLE 1 The hydrogen content in a hydrogen/nitrogen mixture, expressed by mole fraction, is x(H ) = 0,1.
2
EXAMPLE 2 The sulfur dioxide content in air at 101,325 kPa and 25 °C, expressed by mass concentration, is
3
β(SO ) = 1 mg/m .
2
Gas mixture composition may either relate to the preparation of gas mixtures or to the analysis of gas
mixtures. In the first case, the composition expresses the formulation of a prepared mixture. Here the
components are the parent gases that were mixed. These can be technically pure gases or specified gas
mixtures. In the second case, the composition expresses the results of analysis. Here the components are the
6 © ISO 2003 — All rights reserved

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ISO 14912:2003(E)
analytes (i.e. the distinct chemical substances determined quantitatively) and the matrix (i.e. the
complementary gas).
Fractions are often used in the expression of results of gas mixture preparation. If a gas mixture consists of N
components, 1, 2, ., N, and if the amounts of these components in the mixture are quantified by amount of
substance, n , n , ., n , the mole fraction x of any component i is given by
1 2 N i
n
i
x = (3)
i
n
k

k
If the amounts of the mixture components are quantified by mass, m , m , ., m , the mass fraction w of any
1 2 N i
component i is given by
m
i
w = (4)
i
m
k

k
If the amounts of the mixture components are quantified by volume, V , V , ., V , the volume fraction φ of
1 2 N i
any component i is given by
V
i
φ = (5)
i
V
k

k
Concentrations are often used to express the results of mixture analysis. If the amount of a specified analyte,
i, found in the analysed sample is quantified by amount of substance, n , and if V is the sample volume at
i S
specified pressure and temperature, the mole concentration (amount-of-substance concentration) c is given
i
by
n
i
c = (6)
i
V
S
If the analyte amount is quantified by mass, m , the mass concentration β is given by
i i
m
i
β = (7)
i
V
S
If the analyte amount is quantified by volume, V , the volume concentration σ is given by
i i
V
i
σ = (8)
i
V
S
In all the above expressions, it has to be noted that the sample volume depends on pressure and
temperature. In the expression for the volume concentration, the analyte volume also depends on pressure
and temperature. For both volumes, the state conditions have to be the same.
The quantities of composition exhibit different behaviour concerning the dependence on pressure and
temperature, as follows:
 mole concentration and mass concentration depend strongly on state conditions,
 volume fraction and volume concentration depend weakly on state conditions,
 mole fraction and mass fraction are strictly independent of state conditions.
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ISO 14912:2003(E)
The quantities above are primarily intended for describing the composition of gas mixtures which are
homogeneous and stable. In a technical sense, they may also apply to both heterogeneous and unstable
mixtures but that is not their intended usage in this International Standard (see below).
Given the restriction to homogeneous gas mixtures, the main implication for this International Standard is that
the state conditions (pressure and temperature) shall be such that the mixture is completely gaseous. This
requirement applies to all the quantities. In addition,
a) the volume concentration is only applicable if the state conditions are such that the individual component
under consideration, before mixing, is completely gaseous, and
b) the volume fraction is only applicable if the state conditions are such that all components, before mixing,
are completely gaseous.
The expression “completely gaseous” means, for an individual component, that the pressure is well below the
saturation pressure at the given temperature or that the temperature is well above the critical temperature. For
a mixture, the equivalent condition is that the pressure is well below the dew pressure at the given
temperature or that the temperature is well above the cricondentherm. In other words, the state conditions are
to be well outside the relevant condensation regions. Methods for assessing whether, at specified state
conditions, gas mixtures and their components are completely gaseous are described in Annex A.
If the restriction to homogeneous and stable mixtures cannot be guaranteed, then the way forward is
inevitably complex. For instance, if the gas mixture is not stable at the relevant state conditions, i.e. if chemical
reactions between mixture components take place, then the composition depends u
...

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